CN102145302A - Method for preparing recyclable chiral catalyst and application thereof - Google Patents
Method for preparing recyclable chiral catalyst and application thereof Download PDFInfo
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- CN102145302A CN102145302A CN2011100286560A CN201110028656A CN102145302A CN 102145302 A CN102145302 A CN 102145302A CN 2011100286560 A CN2011100286560 A CN 2011100286560A CN 201110028656 A CN201110028656 A CN 201110028656A CN 102145302 A CN102145302 A CN 102145302A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a method for preparing a recyclable chiral catalyst and application thereof. The method comprises the following steps of: stirring acetic acid solution of polyvinyl alcohol or dimethyl formamide solution of polyacrylonitrile and a certain amount of proline or proline derivative uniformly, then putting the mixture into an injector, and performing electrostatic spinning to prepare a fiber membrane of a nano structure, wherein the spinning voltage is 10kV and the receiving distance is 15 centimeters; performing vacuum drying on the membrane at the temperature of between 60 and 100 DEG C to obtain a proline carried nano fiber membrane, then stirring the obtained membrane in dichloromethane solution of triethylamine for half an hour, and performing vacuum drying to obtain the catalyst; and sealing and storing the catalyst for later use.
Description
Technical field:
The invention belongs to the synthetic field of physical chemistry, be specifically related to a kind of preparation method and application thereof of callable chiral catalyst.
Background technology:
The optics chiral material, except that from natural, artificial synthetic is main approach.The catalysis asymmetric reaction not only can provide the key technology of optical homochiral material preparation, and belongs to eco-friendly green synthesis method.The chiral catalyst of development high efficiency, high selectivity, high yield has become the key problem of development chiral technology.Chiral organic micromolecule catalyst is the important chiral catalyst of the 3rd class after chiral transition metal and biocatalyst.Chiral organic micromolecule catalyst has following superiority: 1. organic molecule catalysis can effectively avoid heavy-metal residual to the particularly pollution problem of drug products of product on the one hand.2. have synthetic simple, mild condition, plurality of advantages such as easy to operate, nontoxic.But the synthetic and not recyclable property of micromolecule catalyst self has also been brought burden to reaction cost, and the heterogeneous catalysis of support type can improve catalyst utilization when not reducing the catalyst activity, and the preparation method who therefore studies callable support type chiral catalyst has very important meaning.
Summary of the invention:
A first aspect of the present invention purpose is to provide a kind of preparation method of callable chiral catalyst newly.The catalyst that this method makes has advantages of higher stability and activity, can activity remain unchanged substantially after reusing three times.
The technical scheme that the present invention takes for achieving the above object is as follows, a kind of preparation method of callable chiral catalyst, it is characterized in that, may further comprise the steps: use the acetic acid solution of polyvinyl alcohol or the dimethyl formamide solution of polyacrylonitrile, stir with proline or proline derivative, put into syringe then, carry out the tunica fibrosa that electrostatic spinning is made nanostructured, spinning voltage 10kV, receiving range 15cm; Then the film that makes is obtained the nano fibrous membrane of proline load 60-100 ℃ of following vacuum drying, then the film that obtains is stirred half an hour in the dichloromethane solution of triethylamine, vacuum drying obtains catalyst again.
The acetic acid solution of described polyvinyl alcohol is the acetic acid solution of 7%-10% polyvinyl alcohol content;
The dimethyl formamide solution of described polyacrylonitrile is the dimethyl formamide solution of 7%-10% polyacrylonitrile content.
Another aspect of the present invention purpose provides the application of the asymmetric aldol condensation reaction that a kind of above-mentioned catalyst that makes undertakies by benzaldehyde derivative and acetone in catalysis, the callable loaded catalyst that adopts method for preparing of the present invention to obtain, can obtain extraordinary catalytic effect, and repeated use still can obtain good catalytic effect after reclaiming.
Described benzaldehyde derivative is 4-chloro-benzaldehyde, to cyanobenzaldehyde, P-methoxybenzal-dehyde, paranitrobenzaldehyde, p-tolyl aldehyde.
The catalytic reaction chemical equation is as follows:
Description of drawings:
The sem photograph that the amplification of the nanofiber film catalyst of Fig. 1 proline load is 10000 times (ESEM is the S-4800 field emission scanning electron microscope of Hitachi);
Fig. 2 is liquid chromatogram (the Agilent liquid chromatogram 1200 of product (4R)-4-(4 '-cyano-phenyl)-4-hydroxyl-2-butanone, flowing is n-hexane mutually: isopropyl alcohol: diethylamine (volume ratio)=75/25/0.1, flow velocity: 1.00mL/min, wavelength 254nm).
The specific embodiment:
Embodiment 1: the nanofiber film catalyst of preparation proline load
The L-proline of the acetic acid solution of 10g7% polyvinyl alcohol content and 0.07g stirs, and puts into syringe then, carries out the tunica fibrosa that electrostatic spinning is made nanostructured, spinning voltage 10 kV, receiving range 15cm.Then film is obtained the nano fibrous membrane of proline load 60 ℃ of following vacuum drying, then the film that obtains is stirred half an hour again in the dichloromethane solution of triethylamine, obtain catalyst 70 ℃ of following vacuum drying again.
Embodiment 2: the condensation reaction of catalysis 4-cyanobenzaldehyde and acetone
(1mmol 131mg) is dissolved in the acetone (5mL) the 4-cyanobenzaldehyde, adds 0.25g proline film catalyst, stirs under the room temperature, and is complete up to aldehyde reaction.Use saturated NH
4The Cl dilution, ethyl acetate extraction.The organic layer anhydrous magnesium sulfate drying boils off the solvent column chromatography then and obtains product (4R)-4-(4 '-cyano-phenyl)-4-hydroxyl-2-butanone, and productive rate 88.2% and ee value are 71.8%.
Embodiment 3: the recycling of catalyst:
Reuse 3 times with acetone cleaning, drying, activation back by the catalyst after catalyst reaction among the embodiment 2 is reclaimed, detect its catalytic activity as shown in Table 1, as can be seen from Table I, the nanofiber film catalyst of proline load of the present invention, after reusing 3 times, its catalytic efficiency does not have to reduce substantially, and concrete data see the following form.
Table one: the catalytic efficiency statistical form after catalyst is reused
| Batch | Productive rate % | ee% |
| Use for the 1st time | 87.6% | 71.2% |
| Use for the 2nd time | 87.1% | 70.6% |
| Use for the 3rd time | 85.8% | 69.9% |
Claims (5)
1. the preparation method of a callable chiral catalyst, it is characterized in that, may further comprise the steps: use the acetic acid solution of polyvinyl alcohol or the dimethyl formamide solution of polyacrylonitrile, stir with proline or proline derivative, put into syringe then, carry out electrostatic spinning and make the tunica fibrosa of nanostructured, spinning voltage 10kV, receiving range 15cm; Then the film that makes is obtained the nano fibrous membrane of proline load 60-100 ℃ of following vacuum drying, then the film that obtains is stirred half an hour in the dichloromethane solution of triethylamine, vacuum drying obtains catalyst again.
2. the preparation method of a kind of callable chiral catalyst according to claim 1, it is characterized in that: the acetic acid solution of described polyvinyl alcohol is the acetic acid solution of 7%-10% polyvinyl alcohol content.
3. the preparation method of a kind of callable chiral catalyst according to claim 1, it is characterized in that: the dimethyl formamide solution of described polyacrylonitrile is the dimethyl formamide solution of 7%-10% polyacrylonitrile content.
4. the application of the asymmetric aldol condensation reaction undertaken by benzaldehyde derivative and acetone in catalysis of the described chiral catalyst of claim 1～3.
5. the application of the asymmetric aldol condensation reaction that chiral catalyst according to claim 4 is undertaken by benzaldehyde derivative and acetone in catalysis is characterized in that: reacted chiral catalyst with acetone clean, drying, use again through overactivation then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201110028656A CN102145302B (en) | 2011-01-27 | 2011-01-27 | Method for preparing recyclable chiral catalyst and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110028656A CN102145302B (en) | 2011-01-27 | 2011-01-27 | Method for preparing recyclable chiral catalyst and application thereof |
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| CN102145302A true CN102145302A (en) | 2011-08-10 |
| CN102145302B CN102145302B (en) | 2012-10-03 |
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| CN201110028656A Expired - Fee Related CN102145302B (en) | 2011-01-27 | 2011-01-27 | Method for preparing recyclable chiral catalyst and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103285921A (en) * | 2013-06-09 | 2013-09-11 | 东南大学 | Silicone rubber immobilizing organic catalyst as well as preparation method and application thereof |
| CN111893584A (en) * | 2020-06-16 | 2020-11-06 | 杭州千芝雅卫生用品有限公司 | Water-resistant environment-friendly fiber filter material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569254A (en) * | 2004-05-12 | 2005-01-26 | 天津大学 | Nanometer ultrafine fibre film material of chitose and its preparation method |
| CN1827573A (en) * | 2006-04-11 | 2006-09-06 | 武汉大学 | Process for preparing optically active beta-hydroxyketone |
| CN101352693A (en) * | 2007-07-27 | 2009-01-28 | Gkss-盖斯特哈赫特研究中心有限责任公司 | Immobilized homogeneous catalysts |
| WO2009015804A1 (en) * | 2007-07-27 | 2009-02-05 | Basell Polyolefine Gmbh | Catalyst system for polymerization of olefinic monomers, process for preparing polymers and polymers prepared by the process |
| US20100230339A1 (en) * | 2005-12-19 | 2010-09-16 | Evolved Nanomaterial Sciences, Inc. | Particulate chiral separation material |
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2011
- 2011-01-27 CN CN201110028656A patent/CN102145302B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569254A (en) * | 2004-05-12 | 2005-01-26 | 天津大学 | Nanometer ultrafine fibre film material of chitose and its preparation method |
| US20100230339A1 (en) * | 2005-12-19 | 2010-09-16 | Evolved Nanomaterial Sciences, Inc. | Particulate chiral separation material |
| CN1827573A (en) * | 2006-04-11 | 2006-09-06 | 武汉大学 | Process for preparing optically active beta-hydroxyketone |
| CN101352693A (en) * | 2007-07-27 | 2009-01-28 | Gkss-盖斯特哈赫特研究中心有限责任公司 | Immobilized homogeneous catalysts |
| WO2009015804A1 (en) * | 2007-07-27 | 2009-02-05 | Basell Polyolefine Gmbh | Catalyst system for polymerization of olefinic monomers, process for preparing polymers and polymers prepared by the process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103285921A (en) * | 2013-06-09 | 2013-09-11 | 东南大学 | Silicone rubber immobilizing organic catalyst as well as preparation method and application thereof |
| CN111893584A (en) * | 2020-06-16 | 2020-11-06 | 杭州千芝雅卫生用品有限公司 | Water-resistant environment-friendly fiber filter material and preparation method thereof |
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| CN102145302B (en) | 2012-10-03 |
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